Preparation suitable for developing dyeings



Patented v UNITED STATES PATENT OFFICE HANS 0F AND KARI; SCHNITZSP-HN 0F OFFENBAVCH-ON-THE- IAIN, GERMANY, ASSIGNORS, BY MIESNE- ASSIGNMENTS, TO GENERAL ANILINH "WORKS, ING, OF NEW YORK, NZ. Y A. CORPORATION OF DELAWARE PREPARATION SUITABLE son DEVELOPING- nvmes No Drawing. Application filed August 12, 1925, Serial No. 49,818, and in Germany Augustlfi, 1924.

We have found that dry stable prepara-.

tions for making developingbaths can be obtained by mixing an aromatic amine capable of being diazotized in a dry solid form which expression is meant to comprise solid aromatic amines and solid neutral and acid salts of aromatic amines, with a dry nitrite. The salts of the amines may be formed with mineral or other acids and N -sulfonic acids of the amines or their salts may also be employed. If desired, the mixture may contain in addition acompound of an acid character, such for example as an alkali metal bisulfate, naphthalene-tri-sulfonic' acid, solid mineral or organic acids and the like. Such add1- tions may also advantageously be made if an acid salt of an aromatic amine is used. The

mixture may also consist of or be made froman amine capable of being diazotized and a dry solid acid substance and a nitrlte; m such a, case the amine 'will be transformed to a salt when the preparation is dissolved in water. The mixture need not be totally free from water.

It is. often to be preferred to add to the mixture a dry and indiiferent dilutlng agent as sodium sulfate, common salt, more or less dehydrated aluminium sulfate or alum, or 1 magnesium chlorid, salts of aryl-sulfonic acids and the like.

The mixtures composed'as above stated in most cases when dissolved in water give a diazo solution capable of being used for developing urposes without any further treatment. If the aromatic amine is present as such or as a neutral salt and there is no addition of an acid compound, or only so much thereof as is suflicient for forming a neutral salt, the mixture must be dissolved in a dilute acid instead of water.

An addition of some mineral or other acid to the water used for dissolving the preparation should also be made when the salt of the amine is readily hydrolyzed as in this case the formation of the diazo compound goes on more rapidly.

For applying the said mixtures with the best advantages it is important that they are readily wetted when introducing same into water or dilute mineral acid and that they do not get rid of this property in storing especially at elevated temperatures. For this reason an addition of an agent furthering the wetting, such as Turkey red oil, condensation products of formaldeh de with phenolor naphthalenessulfonic aci s, salts, of alkylnaphthalene-sulfonic acids and the like are very useful. Further compounds used in dyeing, for example copper of chromium salts or other auxiliaries in dyeing may be added.

The nature of this invention will be more fully explained b the following examples to which however t e invention is not limited.

parts 0 sodium bisulfate, parts of Glaurs salt, all free from water, are well mixed, whereupon a mixture of 60 parts of sodium sulfate with 7 parts of sodium nitrite is added by portions.

diazo solution ready for use when dissolved in cold water. The mixture is very stable if protected from moisture. Instead of Glaubers salt other indifi'erent salts such as common salt ma be employed. The quantity of sodium bisu fate may be varied, or this salt may be left out or substituted by other acid The preparationobtained forms at once a substances totally or partially. Instead of the aniline-hydro-sulfate, the hydrochloride may also be em loyed; in this case the quantit of sodium isulfate should be increased.

11 a similar manner developing preparations at once ready for use can be obtained from other aromatic amines, as paratoluidin or meta-xylidin.

' diazo solution shortly after dissolving the mixture.

Ezmmple 3 180 parts of alpha-naphthyl-amine hydrochloride with an addition of 2 parts of Turkey red oil (for assisting the wettin are mixed with 465 parts of the dry tecdmical naphthalene-LG-disulfonic acid sodium salt and then with 70 parts of dry sodium nitrite. The mixture thus obtained is very stable even when stored at 60 degrees to degrees centirade. Instead of the alpha-naphthyl-amineydrochloride, a corresponding quantity of the nitrate can be employed as well.

Ewample 4 178 parts of 4-chloro-2-amino-1-toluenehydrochloride are mixed first with 452 parts of a mixture of the sodium salts of naphthalene-tri and -tetra-sulfonic acid (obtained by sulfonating 1 molecule of naphthalene with 4 molecules of sulfur trioxid) and then with 7 0 parts of dry sodium nitrite.

EwmpZe 5 285 parts of tolidin-hydrochloride are milled with 200 parts of partlydesiccated aluminium sulfate (molecular weight 500 instead of 667) and with 435 parts of the sodium salt of 2.7-naphthalene-disulfonic acid. Then 140 parts of dry sodium nitrite are added.

Ezmmple 6' 17 5 parts of para-nitraniline-hydrochloride are mixed with 355 parts of technical 1.6- naphthalene-disulfonic acid sodium salt, and parts of dry sodium nitrite.

Ezvample? 69 parts of para-nitraniline are stirred into 79 parts of sulfuric acid (94 per cent strength). After the sulfate is formed 50 parts'of partly dehydrated aluminium sulate are worked into the mass. The mixture soon becomes dry and is then mixed with 100 parts of dry naphthalene-tri-. and -tetra-sulfonic acid sodium salt, as obtained by sulfonating 1 molecular proportion of naphthalene with 4 molecular proportions of sulfur trioxid. Finally, 35 parts of sodium nitrite are added and the whole mass is ground until uniform.

Instead of para-nitraniline, other aromatic nitro-amino-compounds can be used.

Example 8 82 parts of dry ortho-chloro-aniline-hydrochlor1de are milled first with 183 parts of partly dehydrated aluminium sulfate and then with 35 parts of dry sodium nitrite. A

product rather nonhygroscopic and very stable also when stored in a'warm room, is

obtained which when dissolved in dilute hydrochloric acid forms a diazo solution ready for use. a

Example 9 18.3 parts of mono-aniline-oxalate, 80 parts of sodium sulfate, 4.5 parts of oxalic acid and 7 parts of sodium nitrite, all as dry as possible, are mixed. When dissolved in water, a diazo solution ready for use is obtained in a short time.

Instead of oxalic acid, other acid agents suitable to set nitrous acid free from its salts may be used. Sodium nitrite may be replaced by other nitrites, for example those of zinc or barium.

Example 10 About 42 parts of -an acid salt of 1.5-naphthalene-disulfonic acid and para-nitraniline are mixed with 62.6 parts of 2.7 -naphthalenedisulfonic acid sodium salt and 7.2 parts of sodium nitrite. When dissolved in water containing some acid, in a short time a diazo solution ready for use is obtained. Acid compounds such as bisulfate may also be added to the mixture.

Instead of the acid salts, neutral salts can be used, e. g. salts of di-isopropyl-naphthalene-sulfonic acid and so on.

Example 11 7 23.1 parts of alpha naphthylamine-N sulionic acid sodium salt, 25 parts of sodium sulfate and 36 parts of sodium bisulfate, all dehydrated as much as possible, are mixed well and a mixture of 7 parts of dry sodium nitrate and 20 parts of sodium sulfate is then added in portions.

When dissolved in cold water, a diazo solu-' tion ready for use is obtained after a short while. A small addition of mineral acid to the water accelerates the formation of the diazo compound, and the bisulfate may be Ill In a similar way, develfiping preparations can be composed of the sulfonic acids of other amines which also may be nitrated or sulfonated.

Emample 1% A mixture is prepared from 26.3'parts of 3.4-dichloro-benzene-1-sulfaminic acid sodium salt, parts of naphthalene-tri-sulfonic acid sodium salt, 36 parts of sodium bisulfate and 7.2 parts of sodium nitrite. On

dissolving in water the diazo solution 1s ready for use in a short time.

Example 13 I I Example 14 300 parts of 4-chloro-2-amino-1-toluenebenzene-sulfonate are mixed with 388 parts of practically anhydrous magnesium-potassium chlorid (Mg'Cl 2KOl) 240 parts of sodium bisulfate and 72 parts of sodium nitrite.

Similar products are formed with the isomeric chloro-toluidines.

Ewwmple 15 ride are mixed with 151 parts of partly desiccated aluminium sulfate, 120 parts of sodium bisulfate 172 parts of para-toluene-sulfonic acid, and 72 parts of dry sodium nitrite.

Ewample 16 p Example 17 138 parts of para-nitraniline in a fine powder which may be made in a state capable of being readily wetted by an addition of 0.1 part of isopropyl-naphthalene-sulfonic acid 175 parts of para-nitraniline-hydrochlosodium salt, are ground with 180 arts of desiccated magnesium-ammonium-c orid about MgCl .2NH Cl) 300 parts of anhyrous sodium bisulfate and 72 parts of dry sodium nitrite.

Instead of para-nitraniline, other free amines for example dianisidin, can be used.

We claim:

1. As a solid dry composition of matter, a

mixture of a diazotizable aromatic amine in a dry solid form with about an equimolecular proportion ofa nitrite and a water-soluble neutral salt in a dry condition.

2. As a solid dry composition of matter, a dry solid salt of a diazotizable aromatic amine mixed with a nitrite in about equimolecular proportions.

3. As a solid dry composition of matter, a dry solid salt of a diazotizable aromatic amine mixed with a nitrite in about equimolecular proportions and a water-soluble neutral salt in a dry condition.

4. As a solid dry composition of matter, a

mixture of a dry acid salt of a diazotizable aromatic amine, a solid nitrite in about equimolecular proportion to the amine, a watersoluble neutral salt in a dry condition and a solid compound of an acid character.

5. A solid dry composition of matter for use as a developer comprising a dry solid salt of a diazotizable aromatic amine, a nitrite in about equivalent molecular proportion to the amine, a compound furthering the wetting of the mixture, a compound of an acid character and a neutral water-soluble salt in a dry condition.

In testimony ewhereof we have hereunto set our hands.

HANS KRZIKALLA. KARL SCHNITZSPAHN. 

